Hardenable resin composition



Patented Dec. 4, 1945 T OFFICE Arthur Voss, deceased, late ofFranki'ort-on-the- Hedwig Voss, adminis- Main, Germany.

3 Claims.

The present invention. relates to compositions oi matter.

It is known that, owing to their mechanical strength and chemicalresistance, the socalled phenol resins, i. e. condensates from phenolsand formaldehyde, are dominating among the plastics known in the artthough they belong to one of the oldest classes of plastics and thoughthey lack one important property,'namely the clasticity characteristicof a series of new plastics, for instance, polymerization products.

Whereas the polymeric plastics possess an elasticity very similar tothat owned by their natural prototypes, the cellulose and thecaoutchouc, the plastics from phenol and formaldehyde show in theirfinal state, i. e. in the case of hardenable resins in the state ofresites, a comparativelyv small elasticity. Therefore, wherever thisproperty is required in the industry said plastics can hardly. beapplied with success. In this domain, therefore, the phenol resins hadto give way to the highly elastic plastics obtained by polymerization.

Since, however, the polymers do not live up to certain other propertiesof the phenol resins, the problem of preparing elastic phenol resinsbecame more and more urgent; yet all attempts to arrive at a reallysatisfactory solution were without success. One of these attempts,repeated in vain, was the combination of phenol resins with softeners.Most of the softeners, however, had an insufficient compatibility withphenol resins and those which were sufilciently compatible and give riseto an improved elasticity were also not suitable since the improvementattained was again lost when the phenol resin was converted into itsfinal state, i. e. the resite. The ingredients oi the mixture demixedand the masses lost their uniformity and, consequently, their elasticproperties.

Now, we have found that elasticity may be im parted to phenol resins bymixing them, if condensed not further than to the resol state and ofbeing capable of hardening when heated or when mixed with knownhardennig agents, with long-chained aliphatic organic compoundscontaining at least 12 carbon atoms and having in their molecule both anexchangeable, that is to say a reactive, halogen with a hydrophilicgroup or oxygen. Substances of this kind may belong able, for instance,halogenhydrins, that is to say long-chained aliphatic compoundscontaining in their molecule bound to adjacent carbon atoms.

tratrix, Frankfort-on- Karl Diets, Kronberg Thomas, Hoi'heim in T in theAlien Property the-Main, Germany, and in Taunus, and Heinz aunus.Germany; vested Custodian No Drawing. Application May 23,1941, SerialNo.

Germany June 6, 1939 hand, a halogen atom. Furthermore, there are verysuitable, halogen containing polymerizates from vinylchlorideandmethacrylic acid. Instead or vinylchloride, vinylchloracetate may beinterpolymerized with the said monomeric acids. There may, furthermore,be used interpolymerizates from chloromaleic anhydride and vinylcompounds such as styrene or -vinylacetate. In aiithese polymers thehalogen is very reactive.

Such interpolymeiizates are, for instance, de-

scribed in the Patent Specification 2,047,398.

of U. S.

The above mentioned substances; which are all long-chained organiccompounds and possess besides a very reactive halogen atom a hydrophilicgroup, may be incorporated with the phenol-aldehyde resins in variousways. It is possible to add the additional substances during themanufac- -ture of the phenol-aldehyde resins or to admix them to theinitially formed liquid condensates from phenol and aldehyde which areobtained in the usual manner by means of alkaline condensing agents andwhich still are in the resol state. It is also possible to use the saidsubstances as additions to pulverulent masses from which mouldedarticles are to be prepared. Furthermore, the said substances may beadded to known mixtures of phenol and aldehyde which harden in the coldor to liquid pre condensates from phenol and aldehydes with simultaneousaddition of the usual catalysts of hardening action, especially those ofacid reaction, and/or ad- Juvants improving the chemical resistance.Catalysts of hardening action are described in U, S.

' Patent 2,034,802; for this purpose aromatic sulioto various classesof, compounds; there are suitchlorides are particularly useful.Adjuvants improving the chemical resistance of the said compositions ofmatter aiter hardening are, for instance, aliphatic esters or. theformula CHzCLR where It represents a radical selected from the groupconsisting of CH2C1; CH20H;

CHOH.CHzCl; CHC1.CH2OH and CHCH: I o l a on the one hand, an OH-groupand, on the othe as described and claimed in patent application Theabove mentioned additional substances are, distinguished from allhitherto known agents used for hardening in the cold or for improvingthe elasticity by the fact that they impart to the products considerablybetter elastic properties. These final products may be obtained invarious forms, as masses for preparing shaped or moulded articles or, ifdesired with filling agents, as cement or mortar masses or as lacquersor the like.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto, the parts being by weight:

(1) 80 parts of a normal pulverulent phenolformaldehyde-resin mass aremixed with 20 parts of an interpolymerisate from vinylchloride andmaleic anhydride. This mixture may be used without any further treatmentfor the preparation of moulded articles of all kinds especially by wayof hot-pressing. The elastic properties are essentially better thanthose of the articles obtained from normal phenol-resin masses, withoutthe other known valuable properties of the phenoplasts being reduced.

(2) 90 parts of a liquid artificial resin obtained by condensation ofphenol and formaldehyde are mixed with parts of a chlorhydrin obtainedfrom epichlorhydrin and dodecyl alcohol. The mixture may be hardenedeither by heat or by addition of a substance having a hardening actionin the cold, for instance, an aromatic sulfochloride. An addition ofsofteners, for instance,

benzyl alcohol, is also possible. These mixtures may be used either forlacquer-like paints or for impregnating building material and wood;furthermore, in admixture with filling agents, as

mortar for building masonry, for painting and plastering or forpreparing coatings, adhesives and filling-in masses.

Instead of the above mentioned chlorhydrin there may also be used thechlorhydrin obtained from epichlorhydrin and lauryl alcohol.

(3) 50 parts of a liquid condensation resin obtained from phenol andformaldehyde are mixed with 20 parts of an interpolymer fromvinylchloride and maleic anhydride or of an interpolymer fromchloromaleic anhydride and vinyl acetate as well as with 20 parts of1.3-dichloropropanol and 10 parts of benzyl alcohol. 40 parts. of thismixture are mixed with 10 parts of benzene sulfochloride whereupon thewhole mass hardens by itself in the cold. Instead of benzenesulfochloride there may also be used paratoluene sulfochloride.

The mixtures thus obtained which harden in the cold may be used, withfilling agents, for the preparation of mortars, cements and filling-inmasses or, without filling agents, diluted with solvents for lacquersand impregnations.

We claim:

1. Compositions of matter comprising parts of a heat hardenablephenol-formaldehyde condensation product condensed not further than theresol state and 20 parts of an interpolymerization product of vinylchloride with maleic anhydride.

2. Compositions of matter comprising 80 parts of a heat-hardenablephenol-formaldehyde condensation product condensed not further than theresol state and 20 parts of an interpolymerization product ofvinylchloride with maleic anhydride, an aliphatic ester of the formulaCHaC'LR where It represents a radical selected from the group consistingof benzoyl alcohol and an aromatic sulfochloride,

3. A hardenable composition of matter comprising 80 parts of the heathardenable condensation product of a phenol and an aldehyde in a statenot further advanced than the resol state and 20 parts of a halogencontaining interpolymerizate obtained by copolymerizing mixtures ofmaterials selected from the group consisting of vinyl chloride andmaleic anhydride; vinyl chloracetate and maleic anhydride; vinyl acetateand chloromaleic anhydride; styrene and chloromaleic anhydride.

HEDWIG VOSS,

As Administratria: of Arthur Voss, Deceased.

KARL DIETZ. HEINZ THOMAS.

Certificate of Correction Patent No. 2,390,198. December 4, 1945' ARTHURVOSS, DECEASED It is hereby certified that error appears in the printedspecification of the above numbered patent requiring correction asfollows: Page 2, second column, line 35, for benzoyl read benzyl; andthat the said Letters Patent should be read with this correction thereinthat the same may conform to the record of the case in the Patent Signedand sealed this 28th day of January, A. D. 1947.

LESLIE FRAZER First Assistant Commissioner of Patents.

